Bis-(n-acylamino-phthalimide)-disazo dyestuffs

ABSTRACT

AZO DYESTUFFS FREE FROM SULFONIC ACID GROUPS ARE PREPARED WHICH ARE VALUABLE NEW PIGMENT DYESTUFFS CHARACTERIZED BY GOOD FASTNESS TO LIGHT, SOLVENTS AND MIGRATION, AND BY A GOOD THERMAL STABILITY ADAPTED FOR USE IN COLORING PAPERS, LACQUERS, AND SYNTHETIC MATERIALS AND FOR PRODUCING PIGMENT PASTE AND PRINTING INKS. THE DYESTUFFS CORRESPOND TO THE GENERAL FORMULA   2-((1,3-DI(O=),(K1-N=N-),(R)M-ISOINDOLIN-2-YL)-NH-V-NH-),   WHERE V STANDS FOR A RADICAL-OC-B-CO-OR A RADICAL   1,3-DI(O=),(K1-N=N-),(R)M-ISOINDOLINE   WHERE B DENOTES A DIRECT BOND, AN OPTIONALLY SUBSTITUTED ALIPHATIC, ARALIPHATIC, CARBOCYCLIC OR HETEROCYCLIC RADICAL, X STANDS FOR NH, O OR S; K1 DENOTES THE RADICAL OF A MONOFUNCTIONAL COUPLING COMPONENT; R STANDS FOR IDENTICAL OR DIFFERENT SUBSTITUENTS; AND M IS AN INTEGER FROM 0 TO 3.

United States Patent US. Cl. 260-152 5 Claims ABSTRACT OF THE DISCLOSURE Azo dyestufis free from sulfonic acid groups are prepared which are valuable new pigment dyestuffs characterized by good fastness to light, solvents and migration, and by a good thermal stability adapted for use in coloring papers, lacquers, and synthetic materials and for producing pigment paste and printing inks. The dyestufis correspond to the general formula (R m I )m where V stands for a radical -OCBCO- or a radical where B denotes a direct bond, an optionally substituted aliphatic, araliphatic, carbocyclic or heterocyclic radical, X stands for NH, O or S; K denotes the radical of a monofunctional coupling component; R stands for identical or ditferent substituents; and m is an integer from 0 to 3.

The object of the present invention comprises valuable new azo dyestuifs of the formula in which V stands for a radical -OC-BCO or a radical Rm m I where B means a direct bond, an optionally substituted aliphatic, araliphatic, carbocyclic or heterocyclic radical and X stands for NH, O or S; K denotes the radical of a monofunctional coupling component; R stands for iden- 3,646,004 Patented Feb. 29, 1972 tical or different substituents; and m represents and integer from 0 to 3.

Suitable dyestuffs are, for example, those of the formula o 0 II I m I ll in which B stands for a direct bond, an optionally substituted aliphatic, aralyphatic, carbocyclic or heterocyclic radical; K denotes the radical of a monofunctional coupling component; R stands for identical or dilferent substituents; and m represents an integer from and those of the formula in which X stands for NH, O or S; K denotes the radical of a monofunctional coupling component; R stands for identical or different substituents; and m denotes an integer from 0 to 3.

Suitable aliphatic radicals B are, in particular, straightchain or branched alkylene radicals which may be interrupted by hetero atoms or by carbocyclic radicals, for

example, the radicals H OO Hi- Suitable araliphatic radicals are, in particular, aralkylene radicals.

Suitable carbocyclic radicals are, in particular, optionally substituted phenylene and naphthylene radicals including, phenyl radicals which are linked by bridge members, such as the following, for example:

( )m (III) as well as cycloalkylene radicals, such as A suitable heterocyclic radical is, for example, the radical (R)m (IV) in which K R and m have the same meaning as above,

or their functional derivatives, such as anhydrides, semiesters or neutral esters, with dicarboxylic acid hydrazides of the formula in which B has the same meaning as above,

in a molar ratio 2: 1, optionally in the presence of suitable condensing agents, in a high-boiling, organic solvent, choosing the components so that the final dyestufis are free from sulphonic acid groups. Preferred compounds (IV) are those of the formula COO1I (tom -COOH (IVa) or their functional derivatives, which yield dyestufis of the formula in which X means NH, or S,

in a molar ratio of 2:1, optionally in the presence of suitable condensation agents, in a high-boiling organic solvent, choosing the components so that the final dyestuffs are free from sulphonic acid groups. Preferred compounds (IV) are those of the Formula IVa or their functional derivatives, which yield dyestuffs of the formula (mm B) m (IIIa) in which K R, m and X have the same meaning as above.

The starting dyestufis of the Formulae H or IIa are obtained in conventonal manner by diazotising the optionally substituted aminophthalic acids or their func tional derivatives and by coupling with monofunctional coupling components.

Preferred dyestuffs are those of the formula in which V is X (1]; -OCBGO orwherein B is a direct bond or a radical selected from the group consisting of alkylene with 1-4 carbon atoms; xylylene cyclohexylene; phenylene; phenylene substituted by 1 or 2 members Cl or N0 biphenylene; naphthylene U or a radical L-- where K is selected from the group consisting of 2-hydroxynaphthoic-acid-anilido; wherein the anilido residue of said 2-hydroxy-naphthoic-acid-anilido is unsubstituted or contains 1-3 substituents selected from the group consisting of methyl, methoxy, ethoxy, nitro, chloro, and acetylamino; 3-methyl-pyrazolonyl-5 which contains one substituent selected from the group consisting of phenyl, chlorophenyl, methylphenyl, nitrophenyl, carbonamido, and carbomethoxy; acetoacetic acid anilido wherein the anilido residue of said acetoacetic acid anilido is unsubstituted or contains 1-3 substituents selected from the group consisting of chloro, methyl, methoxy, ethoxy and nitro; 2-hydroXy-naphthoic-acid-naphthyl-amido; 2-hydroXy-naphthoylaminobenzimidazolonyl; 1 phenyl 3 methyl 5 aminopyrazolyl; acetoacetic acid naphthylamido, acetoacetic acid amino benzimidazolonyl; or acetoacetic acid aminobenzothiozolyl; and Y R is selected from the group consisting of methyl, ethyl,

methoxy, ethoxy, fluoro, chloro, bromo, nitro or trifiuoromethyl; and m is an integer from -3.

Diazo components suitable for the production of the starting compounds (IV) or their functional derivatives are, for example, 3- and 4-amino-phthalic acid, 3-aminophthalic acid dimethyl ester, 3-amino-6-methyl-phthalic acid, 3 amino nitro phthalic acid, 3 amino- 6 methoxy phthalic acid, 3 amino 4 methoxyphthalic acid, 3 amino 6 chloro phthalic acid, 3 amino 5,6 dimethoxy phthalic acid, 4 amino- 3 chloro phthalic acid, 4 amino 5 chloro phthalic acid, 4 amino phthalic acid dimethyl ester, 4 amino- 3 methyl phthalic acid, 4 amino 5 methyl phthalic acid, 4 amino 3 methoxy phthalic acid, 4 amino- 5 methoxy phthalic acid and 4 amino 3,6 dichlorophthalic acid.

Monofunctional coupling components K H which can be used are, for example:

2-hydroxy-naphthoic acid- 3 -anilide,

Z-hydroxy-naphthoic acid- (3 -2'-methyl-anilide,

2-hydroxy-naphthoic acid- 3 (4'-methyl -anilide,

2-hydroxy-naphthoic acid- 3 (2-methoxy) -anilide,

2-hydroxy-naphthoic acid- 3 (4'-methoxy )-anilide,

2-hydroxy-naphthoic acid- (3 3 '-nitro -anilide,

2-hydroxy-naphthoic acid- 3 (2'-chloro -anilide,

2-hydroxy-naphthoic acid- 3 (4-chl0ro -anilide,

2-hydroxy-naphthoic acid-( 3 2,4-dimethyl) -anilide,

2-hydroxy-naphthoic acid- 3 2-methyl-5 '-chloro anilide,

2-hydroxy-naphthoic acid- 3 2'-methyl-4'-chloro anilide,

2-hydroxy-n aphthoic acid- (3 (2', S '-dimethoxy-4'- chloro) -anilide,

2-hydroxy-naphthoic acid-(3 2',4'-dimethoxy-5 chloro)-anilide,

2-hydroxy-naphth0ic acid- (3 2'-methy1-4-methoxy) anilide,

2-hydroxy-naphthoic acid- (3 2-methoxy-5'-chloro anilide,

2-hydroxy-naphthoic acid- 3 (2'-methyl-3'-chloro) anilide,

Z-hydroxy-naphthoic acid-(3 )-(naphthyl-(1') )-amide,

2-hydroxy-naphthoic acid-(3 (naphthyl-( 2') )-amide,

Z-hydroxy-naphthoic acid- 3 (2-ethoxy) -anilide,

2-hydroxy-naphthoic acid-( 3 (4'-ethoxy) -ani1ide,

2-hydroxy-naphthoic acid- 3 2-methoxy-5 -methyl anilide,

2-hydroxy-naphthoic acid- (3 (4-acetyl-amino) -anilide,

5- (2,3 '-hydroxy-naphthoyl-amino -benzimidazolone,

1-phenyl-3 -methyl-pyrazolone-5 l- (4'-chlorophenyl -3-methyl-pyrazolone-5,

1- (4'-methylphenyl) 3 -methyl-pyrazolone-5,

l- 3 -nitrophenyl) -3-methyl-pyrazolone-5,

1-(2'-chlorophenyl)-3-methyl-pyrazolone-5,

1-phenyl-pyrazolone-5-carboxylic acid-3-amide,

1-phenyl-pyrazolone-5-carboxylic acid-S-methyl ester,

1-phenyl-3 -methyl-5-amino-pyrazolone.

Acetoacetic acid anilide, acetoacetic acid-Z-chloro-anilide, acetoacetic acid 2,4- dimethyl-anilide, acetoacetic acid-Z-methyl-anilide, acetoacetic acid-2,5-dimethoxy-4- chloro-anilide, acetoacetic acid-Z-methoxy-anilide, acetoacetic acidnaphthyl-(1)-amide, acetoacetic acid-Z-methyl-3-chloro-anilide, acetoacetic acid-Z-methyl-4-chloro-anilide, acetoacetic acid-2,4-dichloro-anilide, acetoacetic acid- 2-nitro-4-chloro-anilide, acetoacetic acid-2-nitro-4-methyl-anilide, acetoacetic acid-2-nitro 4 methoxy-anilide, acetoacetic acid-4-ethoxy-anilide, acetoacetic acid-2-(6- ethoxy-benzothiazolyl)-amide, 5-acetoacetyl-amino-benzimidazolone.

The condensation of the azo compounds (IV) or (IVa) with compounds of the type (V) or (V1) is preferably carried out in a high-boiling organic solvent and in the presence of dehydrating agents. The condensation is performed, for example, at an elevated temperature, generally ranging from to 240 C., but preferably from C. to 180 C., optionally under pressure.

Suitable compounds of the Formula V are, for example:

Oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 4- chloro-isophthalic acid dihydrazide, 2,5-dichloro-terephthalic acid dihydrazide, 3-nitro-terephthalic acid dihycinic acid dihydrazide, adipic acid dihydrazide, terephdrazide, naphthalene-2,6-dicarboxylic acid dihydrazide, cycylohexane-1,4-dicarboxylic acid dihydrazide, thiophene- 2,5-dicarboxylic acid dihydrazide, stilbene-dicarboxylic acid-4,4'-dihydrazide, azobenzene-dicarboxylic acid-4,4- dihydrazide, diphenyl-dicarboxylic acid-4,4-dihydrazide, diphenyl ether-dicarboxylic acid-4,4'-dihydrazide, benzanilide-dicarboxylic acid-4,4-dihydrazide and diphenylmethane-dicarboxylic acid-4,4'-dihydrazide.

Suitable compounds of the Formula VI are, for example, N,N-diamino-guanidine, carbo-bishydrazide and thiocarbonhydrazide.

High-boiling, organic solvents suitable for the condensation of (IV) or (-IVa) or their functional derivatives, for example of the corresponding anhydrides, with (V) or (VI) are, for example, the following solvents boiling above 80 C.: benzene, toluene, xylenes, chlorobenzene, 0-, m-, p-dichlorobenzene, trichlorobenzenes, quinoline, nitrobenzene, glacial acetic acid, cyclohexane, 1,2,3,4-tetrahydro-naphthalene, naphthalene, tetrachloroethylene, anisole, diphenyl ether, di-n-butyl ether, decalin, and mixture of such solvents. Dehydrating agents to be concurrently used are preferably the following, for example: formic acid, acetic acid, propionic acid, anhydrous sodium acetate, zinc chloride, iron(III) chloride, aluminium chloride and boron trifluoride.

For the reaction of the monoazo dyestuffs (IV) or (IVa) or their anhydrides with compounds (III), (V) or (VI) the exact molar ratio 2:1 is to be chosen in order to obtain compounds (I) which are not contaminated with monoazo dyestuffs (III) or (Illa). Dependent upon the use of the same or different compounds (IV) or (-IVa), symmetric or asymmetric dyestuffs of the Formula I can be synthetised.

The products which can be obtained according to the present process are valuable new pigment dyestuffs which are, quite generally, characterised by good fastness to light, solvents and migration and also by a good thermal stability in substrates of the greatest variety. They are used for the colouring of paper, lacquers and synthetic materials, such as, for example, of plasticiser-containing polyvinyl chloride, polyethylene and acrylonitrile/butadiene styrene coand graft-polymers, and for the production of pigment pastes and printing inks.

The parts in the following examples are parts by Weight, the temperatures are given in degrees centigrade.

EXAMPLE 1 9.7 parts of the monoazo dyestuff obtained from diazotised 3-amino-phthalic acid and 2-hydroxy-naphtoic acid-(3)-(4'-methoxy)-anilide are heated at 100 for 30 minutes in a mixture of 200 parts chlorobenzene and 20 parts glacial acetic acid. 1.94 parts terephthalic acid dihydrazide are then added and the mixture is heated at for a further 5 hours. The product is then filtered off with suction while hot, washed first with parts of hot chlorobenzene, then with 100 parts of cold methanol and dried at 50 in a circulating air drying chamber. The yield amounts to 8.9 parts of a Bordeaux pigment which 7 8 is fast to light and top finishes and corresponds to the EXAMPLE 3 formula 9.7 parts of the pigment dyestnfi obtained from di- H O Q-QNH-Q c on ll H OO-NH-0C 011 N=N o NHNCO -CONH EXAMPLE 2 azotised 4-arnino-phthalic acid and 2-hydroxy-naphthoic acid-(3)-(2'-rnethoxy)anilide are heated at 100 for 30 9.4 ts of the a o d e tufi obtained rom diazotised par Z y S f minutes in a mixture of 150 parts o-dichlorobenzene and 3-amino-phthalic acid and Z-hydroxy-naphthoic acid-(3)- 25 (2' methy1) ani1ide and 174 parts adipic acid dihydra oarts glacial acetic acid. 2.7 parts 2,5-dichloro-tereph- Zide are heated at for 4 hours in a mixture of 200 thahc acid dihydrazide are then added and the mixture is parts quinoline and parts glacial acetic acid, the pigkept a a further 3 hours: e product is filtered ment is filtered oil with suction at 100, washed with Off With SHCHOII hile 110i, Washed wlth Warm quinoline equal portions of 200 parts quinoline and benzene, and and methanol, and dried at The yield amounts to dried at in a vacuum until the weight remains con- 9.5 parts of a red pigment dyestufi of the formula OCH;

O 1 CI N=N NNH0 C C O-NH7 Y of 0011 Q-NH-O 0 OH O l N=N G N/ stant. There are obtained 10.2 parts of a bluish red pig- Valuable pigments are likewise obtained when the ment which is resistant to solvents and has the constitudiazo, coupling and imidation components mentioned in tion Examples 1-3 are replaced with the components set out in the following table,

which yields pigments of the specified shades.

while hot, washed first with chloro-benzene, then with methanol and dried at 50". There is obtained in a good Diazo component Coupling component 3-amIiDno-phtha1ic acid 2-hy giroxy-naphtkoic acid- (3) -anilide Imidation component Shade Red. Red.

Red. Red.

Adipic acid dihydrazide Terephthalic acid dihydrazide.

Do 4-amino5-methoxy-phthalic acid-..

o do

Do t .do 3-arnino-phthalic acid 5-acetoacetylam Do. .do A-amino-phthalic acid do Do do Do. .do

Do l-phgnyLB-methyl-pyrazol 2,5-dichioro-terephthalic acid dihydl azide Oxalic acid dihydrazide Succinic acid dihydrazide" Terephthalic acid dihydrazide 4,4'-diphenyl-dicarboxylic acid dihydrazida Oxalic acid dihydrazide Malonic acid dihydrazide Succinic acid dihydrazide Terephthalic acid dihydrazlde 2,5-dichloro-terephthalic acid dihydrazide Oxalic acid dihydrazide Malonic acid dihydrazide Adipic acid dihydrazide 2,5-dichloro-terephthalic acid dihydrazide. Oxalic acid dihydrazide Malonic acid dihydrazide.-.

Terephthalic acid dihydrazide 2,5-dichloro-tcrephtha1ic acid dihydra Oxalic acid dihydrazide Succinic acid dihydrazide. Naphthalcne-2,6-dicarboxylic acid dihydrazide Adipic acid dihydrazide Oxalic acid dihydrazide. Malonic acid dihydrazide Adipic acid dihydrazido. Suberic acid dihydrazidc Oxalic acid dihydrazide. Succinic acid dihydrazide. Adipic acid dihydrazide Suberic acid dihydrazide Oxalic acid dihydrazide- Malonic acid dihydrazide. Red. Succinic acid dihydrazide. Red. Adipic acid dihydrazide.-. Red. Suben'c acid dihydrazide" Red. Oxalic acid dihydrazide Red. Succinic acid dihydrazide. Red. Adipic acid dihydrazide Red Terephthalic acid dihydrazide- Oxalic acid dihydrazide Do. Succinic acid dihydrazide Do. Terephthalic acid dihydrazide Do. Adipic acid dihydrazide Do. Terephthalic acid dihydrazide Do. 2,5-dichloro terephthalic acid dihydrazide. Do Oxalic acid dihyrdazide Do. Adipic acid dihydrazide. D0. Oxalic acid dihydrazide. Do. Malonic acid dihydrazide. go. 0.

Succinic acid dihydrazide. Do. Terephthalic acid dihydraz Do.

Naphtha1ene-2,6-dicarboxyi D0. Oxalic acid dihydrazide Do. Malonic acid dihydrazide. Do. Snccinic acid dihydrazide Do. Terephthalic acid dihydrazid D0. Oxalic acid dihydrazide Do Malonic acid dihydrazide. Do. Terephthalic acid dihydrazid Do. Oxaiic acid dihydrazide Do. Succinic acid dihydrazide. Do. Adipic acid dihydrazide Do.

EMMPLE 4 10.1 parts of the dyestutf obtained from diazotised 3-aminophthalic acid and Z-hydroxy-naphthoic acid-3-a- 70 naphthylarnide are heated at 100 for 30 minutes in a mixture of 150 parts o-dichlorobenzene and 15 parts glacial acetic acid. 1.9 parts terephthalic acid dihydrazide are then added and the mixture is heated at 120 for a further 3 hours. The product is filtered 01f with suction 75 yield a bluish red dyestuif which yields, when incorporated into organic lacquers or synthetic materials, clear dyeings of very good fastness to light, top finishes and migration.

EXAMPLE 5 8.0 parts of the monoazo dyestuff obtained from diazotised 3-amino-phthalic acid and 1-(2-chlor0phenyl)- 3-methyl-pyrazolone-(5) are heated at 100 for 30 min- 11 utes in a mixture of 200 parts chlorobenzene and '20 parts glacial acetic acid. 0.9 part carbobishydrazi'de are then added and heating is continued at 1l0-120 for 5 hours. The product is filtered oil. with suction while hot, washed 12 acid-(3) -(4'-methoxy) -anilide are heated in a mixture of 200 parts chlorobenzene and 20 parts glacial acetic acid at 100 for 30 minutes. 0.9 part carbo-bishydrazide are then added and heating is continued at 120 for 5 hours.

with 150 parts of hot chlorobenzene, then with 100 parts 5 The mixture is suction-filtered while hot, the filter resmethanol, and dried. There are obtained 8.1 parts of a yellow pigment dyestufi' of -the"frmula M u ii 0 c n i ii N CH H 6 N N 0: O N N l 1 which is fast to light and migration.

EXAMPLE 6 9.26 parts of the monoazo dyestuff obtained from diazotised 3-amino-phthalic acid and acetoacetic acid-2,5- dimeth0xy-4-chloro-anilide are heated in 200 parts 1,2,4- trichlorobenzene at 150 for 30 minutes. 0.9 part carbobishydrazide are then added, heating is continued at 140- 150 for hours, and the mixture is suction-filtered at 100. The filter residue is washed with 50 parts chlorobenzene, then with 50 parts methanol, and dried. A yellow dyestulf is obtained which, when incorporated with organic lacquers or synthetic materials, has good fastness to light, top finishes and migration. It corresponds to the formula 9.7 parts of the monoazo dyestuff obtained from diidue is washed with parts chlorobenzene, then with ""50'parts'methanol, and-dried: There is obtained, in a a good yield, a brown pigment. dyestuif which has very good fastness to light, top finishes and migration, and

corresponds to the following formula 1 9 G/ I 5 ii i) N i i 1% 11 HO ENH N-("3 i i OCHg OCH EXAMPLE 8 10.1 parts of the dyestufi obtained from diazotized 4- amino-phthalic acid and 2-hydroXy-naphth0ic acid-(3)- a-naphthyl-amide are heated in a mixture of 150 parts over dichloro-benzene and 15 parts glacial acetic acid at for 30 minutes. 0.89 part N,N-diamino-guanidine are then added and heating is continued at for 3 hours. The

azotised 3-amino-phthalic acid and Z-hydroxy-naphthoic 75 product is filtered off with suction while hot, washed with 13 14 hot o-dichlor'o-benzene and methanol, and dried. A red We claim: pigment dyestulf of the formula 1. A10 dyestutfs which are free from sulfonic acid groups and correspond to the general formula 0 0 0 U U l I NH 1 K1N=N N-NHV-NH I N=N-K.

N 1% I in which V is HO if C-NHQ HNC OCBC O- or C- it C a 15 )m 0 lg )m wherein B is a direct bond or a radical selected from the group consisting of alkylene with 1-4 carbon atoms; xylylene cyclohexylene; phenylene; phenylene substituted by 1 or 2 members C1 or N0 biphenylene; naphthylene Obtained.

Valuable pigments are also obtained when the dune, coupling and imidation components stated in Examples 5-8 are replaced with the components set out in the following table, which yield pigments of the specified shades. s

Diazo component Coupling component Dihydrazide Shade 3-amino-phtha1ic acid 3-methyl-pyrazolone-(5) Carbo-bishydrzaide. Yellow. Do 1-phenyl-3-methyl-pyrazolone-(5) Thiomrbohydrazida D0. D0. 1-(2-chloro-phenyl)-3-methyl-pyrazolone-(5) N,N-diamino-guanid D0. D0. l-phenyl-3-methyl-5-amlno-pyrazole Garbo-bishydrazide Do. Do. Acetoacetic acid-2,5-dimethoxy-4-chloro-anili N,N-diamino-g'uanidine Do. Do Acetoacetic acid-2,4-dimethyl-anilide Thiocarbohydrazide. Do. 4-amino-phtha1ic acid 3-methyl-pyrazolone- Do. D o 1-phenyl-3-methyl-pyrazolone-(5 Do. 1-(i-chloro-phenyl)-3-methyl-pyrazolone-(5 do D0. 1-phenyl-py'razoloue-(5)-carboxylic acid-(4)-a N,N-diamino-guanldine Do. fi-ammo-pyrazole Garbo-bishydrazide Do. Acetoacetlc acid-4-chloroanil 2-hydroxy-naphthaic acid-(3)-a N,N-d gu Carbo-bishydrazide Orange. N,N-diamino-guanidine Red. Thiocarbohydrazide Red. Carbo-bishydrazide Orange. N,N-diamino-guanidine Red. Thiocarbohydrazide Red. Carbc-bishydrazide Red. N,N-dlamino-guam'di.ne Red. Thiocarbohydrazide Red. Carbo-bishydrazide Red. N,N-diamino-guanidine Red. do. Thiocarbohydrazide Red. hydroxy naphthoic acid-(3)-(4-methoxy)-anilide N ,N-diamino-guanidine Red-brown.

d Thiocarbohydrazide Do. Garbo-bishydrazide. o. N,N-diamino-guanidine Do. Thiocarbohydrazide Do. Garbo-bishyd1az1de Red. N,N-diamino-guanidine Red. Thiocarbohydrazide Garbo-bishydrazide Red. N,N-diamino-guanidine Red. Thiocarbo-hydrazide Red. Garbobishydrazide Orange N,N-diamino-guanidinc ed. Thiocarbohydrazide. Red. Carb0-bishydrazide Orange N,N-diamino-guanldldn ed. Thiocarbo-hydrazide Garbo-bishydrazide... N ,N-diamin0-guanidine Do d0 ThiocarbohydIaZide..- 4-aminophthalie acid d0 Carbo-bishydrazide D N,N-diamino-guanidine Thiocarbo-hydrazide. Garb o-bishydrazide N,N-diamino-guanidine Red. Thiocarbohydrazide Red. Garb obishydrazide. Red. N,N-d1amino-guanidine Red. Thiocarbohydrazide Red. Carbo-bishydrazide Red-brown. N ,N-diamino-guanidine Do. Thiocarbohydrazide Do. Garb o-bishydrazide Do. N ,N-diamino-guanidine D0. Thiocarbohydrazide D0. Garbo-bishydrazide Brown. N,N-diamino-guanidine Do. Thiocarbohydrazide Do. Carbo-bishydIazide Do. N,N'-diamino-guanidlne Do. Thiocarbohydrazide Do. Garbo-bishydrazide Red. Thiocarbohydrazide Red. Garbo-bishydrazide Red. N,N-diamino-guanidine Red.

Thioearbohydrazide. Red

15 or a radical where L is -CH=CH, N=N--, CONH, -O,

X is NH, S or 0;

K is selected from the group consisting of Z-hydroxynaphthoic-acid-anilido; wherein the anilido residue of said 2-hydroxy-naphthoic-acid-anilido is unsubstituted or contains 1-3 substituents selected from the group consisting of methyl, methoxy, ethoxy, nitro, chloro, and acetylamino; 3-methyl-pyrazolonyl-5 which contains one substituent selected from the group consisting of phenyl, chlorophenyl, methylphenyl, nitrophenyl, carbonamido, and carbomethoxy; acetoacetic acid anilido wherein the anih'do residue of said acetoacetic acid anilido is unsubstituted or contains 1-3 suhstituents selected from the group consisting of chloro, methyl, methoxy, ethoxy and nitro; Q-hydroxy-uaphthoic-acidnaphthyl amido; 2-hydroxy-naphthoylamino-benzirnidazolonyl; 1-phenyl-3-methyl-5-amino-pyrazolyl; acetoacetic acid naphthylamido, acetoacetic acid amino benzimidazolonyl; or ace-toacetic acid aminobenzothiazolyl; and

R is selected from the group consisting of methyl, ethyl,

methoxy, ethoxy, fluoro, chloro, bromo, nitro or trifiuoromethyl; and

m is an integer from 0-3.

2. A20 dyestuffs of claim 1 which correspond to the general formula 0 o I I (min I (R)m wherein B, K R and m are as defined in claim 1.

l6 3. Dyestuffs of claim 2 which correspond to the formula N-NH-CO-B-CO-NH- (mm (Rm) 1O 4. A20 dyestuffs of claim 1 which correspond to the formula 0 0 t X t 15 K1N=N-@: NNHK JNH-N N: =K1

(Rn f (mm 20 5. A20 dyestuffs of claim 4 corresponding to the formula 35 HENRY R. JILES, Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 

